lecture b2 vsepr theoryunicorn/old/h2a/handouts/pdfs/lectureb2.pdf · covalent bond theories...
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Lecture B2VSEPR Theory
Covalent Bond Theories
1. VSEPR (valence shell electron pair repulsion model). A set of empirical rules for predicting a molecular geometry using, as input, a correct Lewis Dot representation.
2. Valence Bond theory. A more advanced description of orbitals in molecules. We emphasize just one aspect of this theory: Hybrid atomic orbitals. Works especially well for organic molecules, which is the reason we don’t scrap it entirely for MO theory.
3. Molecular Orbital theory. The most modern and powerful theory of bonding. Based upon QM.
Covalent Bond Theories
1. VSEPR (valence shell electron pair repulsion model). A set of empirical rules for predicting a molecular geometry using, as input, a correct Lewis Dot representation.
2. Valence Bond theory. A more advanced description of orbitals in molecules. We emphasize just one aspect of this theory: Hybrid atomic orbitals. Works especially well for organic molecules, which is the reason we don’t scrap it entirely for MO theory.
3. Molecular Orbital theory. The most modern and powerful theory of bonding. Based upon QM.
G. N. Lewis tried to develop a geometrical model foratoms and chemical bonding -- but failed.
G. N. Lewis1875-1946
Gillespie and Nyholm devised a simple scheme for geometrybased on the Lewis dot structure (VSEPR).
Valence shell electron pair repulsion (VSEPR) theory is a model in chemistry used to predict the shape of individual molecules based upon the extent of electron-pair electrostatic repulsion. It is also named Gillespie-Nyholm* theory after its two main developers. The acronym "VSEPR" is pronounced "vesper" for ease of pronunciation.
Ronald J. Gillespie1924 -
*Ronald J. Gillespie and Ronald S. NyholmUniversity College, London, 1957.
Living in 3 Dimensions
What role doesgeometry playin chemicalstructure?
AX2
CO2
Linear GeometryO-C-O angle: 180°
Gillespie and Nyholm looked at the structures of molecules of the form AXn:
16 electrons
O=C=O
AX2
Linear GeometryX-A-X angle: 180°
AX3
Trigonal GeometryX-A-X angle: 120°
AX3BF3
Trigonal Planar GeometryF-B-F angle: 120°
F B F
F
24 electrons
AX4
Square Planar Geometry?X-A-X angle: 90°
AX4CH4
Tetrahedral GeometryH-C-H angle: ?
C
H8 electrons
HH
H
AX4
CH4
Tetrahedral GeometryH-C-H angle: 109.47°
from SketchUp
AX4
Tetrahedral GeometryH-C-H angle: 109.47°
from SketchUp
Green Triangle: 1 + 1 = 2Hypotenuse = √2
Gray Triangle: 2 + 1 = 3Hypotenuse = √3Grey Angle = cos-1(√2/√3)
Blue Triangle: Blue Angle = 180 - 2 x GA
VSEPR in Solids: Diamond Structure
Tetrahedral Site SymmetryC-C-C angle: 109.47°
From CrystalMaker
Diamond
Also ZnS
AX4CH4
Tetrahedral GeometryH-C-H angle: 109.47°
C
H8 electrons
HH
H
AX5
Pentagonal Planar Geometry?X-A-X angle: 72°
AX5
PCl5
Trigonal Bipyramidal Geometry
Cl-P-Cl angles: 90,120°
40 electrons
AX6
Hexagonal Geometry?X-A-X angle: 60°
AX6
SF6
Octahedral GeometryF-S-F angle: 90°
48 electrons
AX6VSEPR in Solids: Body Centered Cubic Structure
Octahedral Site SymmetryC-C-C angle: 90°
From CrystalMaker
Gillespie and Nyholm realized that the covalent bonds were arranged so as to minimize overlap:
They also realized that non-bonding electron pairs on the central atom ALSO needed to be included, and actually required MORE relief from overlap.
Thus, the electron pairs around each atom in a molecule tend to be arranged to minimize repulsion - it doesn’t matter whether these electron pairs are in bonds, or are non-bonding lone pairs.
AX3E0
s = 3n = 3m = 0NO3-
Trigonal Planar Geometry
For example:
s is the total number of bonds (n) and lone pairs (m).
O O
AX2E1
s = 3n = 2m = 1
SO2
S18 electrons
AX4E0
s = 4n = 4m = 0
CH4
Tetrahedral Geometry
AX3E1
s = 4n = 3m = 1
Trigonal Pyramidal Geometry
NH3
AX2E2
s = 4n = 2m = 2
H2O
AX5E0
s = 5n = 5m = 0
Trigonal Bipyramidal Geometry
PCl5
Two different positions. Where do the lone pairs go?
This geometry is the strange one...
Two different positions. Where do the lone pairs go?
Axial position:Three 90° angles andOne 180° angle:Average = (3x90 + 180)/4Average = 112.5°
Two different positions. Where do the lone pairs go?
Axial position:Three 90° angles andOne 180° angle:Average = (3x90 + 180)/4Average = 112.5°
Equatorial position:Two 90° angles andTwo 120° angles:Average = (2x90 + 2x120)/4Average = 105°
Axial position:Three 90° angles andOne 180° angle:Average = (3x90 + 180)/4Average = 112.5°
Equatorial position:Two 90° angles andTwo 120° angles:Average = (2x90 + 2x120)/4Average = 105°
Equatorial is observed even though its average angle is smaller!!!
Equatorial is observed even though its average angle is smaller!!!
Conclusion: electron overlapis a nonlinear function ofdistance.
Equatorial position:Two 90° angles andTwo 120° angles:Average = (2x90 + 2x120)/4Average = 105°
AX4E1
s = 5n = 4m = 1
Seesaw Geometry
SF4
AX3E2
s = 5n = 3m = 2
Tee-Shape Geometry
BrF3
s = 5n = 2m = 3
AX2E3
Linear Geometry
I3-
AX6E0
s = 6n = 6m = 0
Octahedral Geometry
SF6
AX5E1
s = 6n = 5m = 1
Square Pyramidal Geometry
ClF5
AX4E2
s = 6n = 4m = 2
Square Planar Geometry
XeF4
AX2
Linear GeometryX-A-X angle: 180°
Dipole Moments
Two examples: BeCl2 and CO2
Both of these are of the AX2E0 format - lineargeometry. Note that single and double bonds both count as one for VSEPR geometries.
We can also predict the existence of a molecular dipole moment from the molecular geometry, and the electronegativities of each element:
We can also predict the existence of a molecular dipole moment from the molecular geometry, and the electronegativities of each element:
the two bond dipoles in BeCl2 cancel(they are equal in magnitude, and opposite in direction)
BeCl2 has no net molecular dipole.CO2 has no net molecular dipole as well.
What about the molecule: BeClBr?
What about the molecule: BeClBr?
the two bond dipoles in BeClBr do not cancel.
BeClBr has a small molecular dipole oriented alongthe molecular axis, and directed towards the Cl.
What about the molecule: BeClBr?
Another example: H2O
The oxygen is surrounded by four electron pairs, twoin sigma bonds and two in lone pairs.The VSEPR group is AX2E2 -- bent geometry.
or
Does H2O have a dipole moment?
104.5o
we perform this vector additionin our heads:
resultant
the tetrahedral electron group geometry requires that the molecular geometry is bent.
The molecular dipole moment bisects the H-O-H bondand is directed towards the oxygen.
104.5o
H2O has a dipole moment of 1.85D
Both Electronegativity differences and Geometry determine the dipole moment of a molecule:
A second molecule with tetrahedral electron group symmetry about the central atom is NH3 (ammonia):
107.0o
VSEPR class: AX3E1.molecular geometry = trigonal pyramidal.
The molecular dipole moment is coincident with the 3-fold axis of the molecule and is directed towards the N.
1.47D
109.5o
VSEPR group: AX4E0molecular geometry = tetrahedral.
methane is non-polar.
A third molecule with tetrahedral electron group symmetry about the central atom is CH4 (methane):
Lone pairs actually need more room, and cause bond angle compression in NH3 and H2O:
H2ONH3CH4
109.5o
a perfecttetrahedron
107.0o 104.5o
1 lone pair 2 lone pairs
Given the formula for a molecule, you should be able to:
1. Produce the best Lewis Dot representation for that molecule, include resonance structures.
2. Determine the formal charge on each atom of your structure(s).
3. Indicate its molecular geometry.
4. Determine whether it is polar or nonpolar.
5. Specify the direction of the dipole moment.
Dipole moments for trigonal bipyramidal geometries:
VSEPR group: AX2E3 = trigonal bipyramidalmolecular geometry = linear and no dipole momentexample: XeF2
VSEPR group: AX3E2 = trigonal bipyramidalmolecular geometry = t-shapedexample: IF3
Dipole bisects lone pair and is directed towards F.
....F
F
F
what about a SINGLE single lone pair - does it choose an equatorial or axial position within a molecule having a trigonal bipyramidal electron group geometry?
VSEPR group: AX4E1 = trigonal bipyramidalmolecular geometry = see-saw
answer: equatorial
dipole directed along lone-pair-A axis.
And remember to include resonance structures!
An example: ozone, O3 (18 electrons):
O........
OO ....
O.. .. ....
O O.. ..
two resonance structures
Ozone, O3 (18 electrons):
VSEPR group: AX2E1 = trigonalmolecular geometry = bentBond angle = 116°
Ozone, O3 (18 electrons):
VSEPR group: AX2E1 = trigonalmolecular geometry = bentBond angle = 116°
Small dipole moment (0.53D), because it's all oxygen.
Hydrocarbons
methane
Hydrocarbons
cyclohexaneC6H12
Hydrocarbons
axial and equatorialhydrogens
Hydrocarbons
chair
boat
two conformationsof cyclohexane
Hydrocarbons
adamantaneC10H16
Hydrocarbons
cyclopentaneC5H10
Hydrocarbons
cyclobutaneC4H8
Hydrocarbons
cubaneC8H8
Hydrocarbons
cyclopropaneC3H6